Process for breaking petroleum emulsions



\ Patented Nov. 28, 1944 UNITED STATES, PATENT OFFICE PROCESS FORBREAKING PETROLEUM EMULSION S Melvin De Groote, University City, andBernhard Keiser, Webster Groves,

Mo., assignors to Petrolite Corporation, Ltd.,vwilmington, De1., acorporation of Delaware No Drawing. Application October 26, 1942, SerialNo. 488,439

Claims. (Cl. 252-334) This invention relates to the treatment ofpetroleum emulsions. and has for its main object, to provide a novelprocess for resolving petroleum emulsions of the water-in-oil type thatare commonly referred to as cut oil," "roily oil, emulsified oil, etc.,and which comprise fine droplets of naturally-occurring waters or brinesdispersed in a more or less permanent state throughout the oil whichconstitutes the continuous phase of the emulsion.

Another object of our invention is to provide an economical and rapidprocess for separating emulsions which have been prepared under conoiland relatively soft waters or weak brines. Controlled emulsiflcation andsubsequent demulsification under the conditions just mentioned is ofsignificant valuein removing impurities, particularly inorganic saltsfrom pipe line oil.

Briefly described, our process consists in sub- -jecting a petroleumemulsion of the water-in-oil type, to the action of a demulsifying agentconsisting of certain amido pyridinium salts of green petroleumsuli'onic acids.

It is well known that one can prepare a variety of amido pyridiniumcompounds, characterized by the following formula:

/Halogen n' radical containing at least 8 carbon atoms and not morethafi 32 carbon atoms, as an integral part of-at least one of theradicals directly linked to the trivalent nitrogen atom. Asillustrations, reference is made to the following species:

in which the acyl radical RC0 is derived from a trolled conditions frommineral oil, such as crude.

of hydrogen atoms and hydroxyethyl radicals,

monocarboxy detergent-forming acid having at least 8 and not more than32 carbon atoms, and D'EN represents a radical derived from aheterocyclic compound of the pyridine series consisting of pyridine,quinoline, isoquinoline, and C-methyl homologues thereof. (See U. S.Patent No.

2,273,181, dated February 17, 1942, to De Groote 8: Keiser, claim 1.)

OKs-NERO 0.3

in which the acyl radical RC0 is derived from a monocarboxydetergent-forming acid having at least 8 and not more than 32 carbonatoms; and D'ENrepresents a heterocyclic compound of the pyridineseries, consisting of pyridine, quinoline, isoquinoline, and C-methyihomologues thereof; and 2! stands forthe monovalent anion of an acid.(See U. S. Patent No. 2,290,417, dated July 21, 1942, to 'De Groote andKeiser cIaim 1.) y

Halogen in which T is a member of the class consisting of hydroxyethylradicals, alkyl radicals, aryl radicals, aralkyl radicals. and alicyclicradicals havingnot more than 22 carbon atoms; the acyl radical RC0 isderived from a monocarboxy' detergent-forming acid having at least 8 andnot more than 32 carbon atoms; and D'EN represents a heterocycliccompound of thepyridine series consisting of pyridine, quinoline,isoquinoline, andC-methyl homologues thereof. (See our copendingapplication Serial No. 415,763, filed October 20, 1941, now U. S. PatentNo 2,329,700, dated September 21, 1943, claim 1.)

Halogen 'r' cal-g ammar.

in which '1 is a-member of the class consisting and T' is a member ofthe class consisting of methyl radicals, ethyl radicals, andhydroxymethyl radicals,-with the proviso that at least one occurrence ofT is a radical of the kind designated, and difi'erentiated from ahydrogen atom; RC0 is an acyl radical derived from a monocarboxydetergent-forming acid having at least 8 and not more than 32 carbonatoms; and DEN represents a heterocyclic compound of the pyridine seriesconsisting of pyridine, quinoline, isoquinoline, and C-linked methylhomologues thereof. (See our co-pending application Serial No. 415,764,filed October 20,. 1941, now U. S. Patent No. 2,329,701, dated September21, 1943, claim 1.)

Halogen OC.'R

in which B is a, divalent aliphatic radical, containing at least one andless than 15 ether linkages; and T is a member of the class consistingof alkyl radicals; aryl radicals; aralkyl radicals; alicyclic radicals;said hydrocarbon radicals having not more than 22 carbon atoms;

hydroxylated aliphatic ether radicals of the type 3.011, where B has itsprevious significance; and hydroxyethyl radicals; and R denotes aradical derived from a detergent-forming monocarboxy acid having atleast 8 and not more. than 32 carbon atoms; and D'EN represents aheterocyclic compound of the. pyridine series consisting of pyridine,quincline, isoquinoline, and C- linked methyl homologues thereof. (Seeour copending application Serial No. 415,765, filed October 20, 1941,now U. S. Patent No. 2,329,- 702, dated September 21, 1943, claim 1.)

Halogen D'QN/ H i T MN Hon '1" wherein T is a hydrocarbon radical havingat least 8 and not more than 32 carbon atoms, and

T is a member of the class consisting of hydrogen atoms, hydrocarbonradicals having less than 8 carbon atoms, and hydrocarbon radicalshaving at least 8 and not more than 32 carbon atoms; and DEN representsa heterocyclic compound of the pyridine series consisting of pyridine,quinoline, isoquinoline, and C linked methyl homologues thereof. (Seeour co-pending application Serial No. 415,766, filed October 20, 1941,now U. S. Patent No. 2,329,703, dated September 21, 1943, claim 1.)

/Halogen D i N\ alkylene.0OC.R'

alkylene.N

G .R n O in which RC0 is the acyl radical of a low molal monocarboxyacid having carbon atoms or less, and R'CO is the acyl radical of adetergentforming monocarboxy acid having at least 18 and not more than32 carbon atoms; and D'EN represents a het-erocyclic compound of thepyridine series consisting of pyridine, quinoline, isoquinoline, andC-linked methyl homologues thereof. (See our co-pending applicationSerial No. 419,082, filed November 14, 1941, now U. S.

Patent No. 2,335,262, dated November 30, 1943. claim 1.)

The manufacture of the compounds above described may be illustrated bythe following reactions:

It is to be noted that the halogen atom previously depicted couldequally well be the anion of any stron acid, particularly a monobasicacid, such as a sulfonic acid. In other words, such sulfonic acid couldbe used to neutralize pyridinein the same way as hydrochloric acid orsome other halogen acid is employed. In the present instance,oil-soluble green petroleum sulfonic acids are employed in such a mannerthat the halogen in the formula previously presented in replaced by theradical DSOs derived from an oil-insoluble green petroleum sulfonicacid. In other words, the previously mentioned formula is suitablyrewritten as follows:

Specifically, then, the compounds herein contemplated may be indicatedby the following 11- lustrations:

DSO:

in which the acyl radical RC0 is derived from a monocarboxydetergent-forming acid having at least 8 and not more than 32 carbonatoms, and D'EN represents a radical derived from a heterocycliccompound of the pyridine series consisting of pyridine, quinoline,isoquinoline, and C-methyl homologues thereof; and D803 is anoil-insoluble green petroleum sulfonic acid radi- 4 radical RC0 isderived from a monocarboxy detergent-forming acid having at least 8 and'not more than 32 carbon atoms; and D ZN represents a heterocycliccompound of the pyridine series consisting of pyridine,quinoline,isoquinoline, and C-methylhomologues thereof; and D803 is anoil-insoluble green petroleum sulfonic acid radical.

Halogen in which '1 is a member ofthe class consisting of hydrogen atomsand hydroxyethyl radicals, and T is a member of the class consisting ofmethyl radicals, ethyl radicals, and hydroxymethyl radicals, with theproviso that at least one occurrence of T is a radical of the kinddesignated, and differentiated from a hydrogen atom; RCO'ls an acylradical derived from a monocarboxy detergent-forming acid having atleast 8 and not more than 32 carbon atoms; and D'EN represents aheterocyclic compound of the pyridine series consisting ofpyridine,quinoline, isoquinoline, and C-linked methyl homologues thereof; andD803 is anoil-insoluble green petroleum sulfonic acid radical.

-at least 8 and notmore than 32 carbon atoms; and D EN represents aheterocyclic compound of the pyridine series consisting of pyridine,quinoline, isoquinoline, and C-linked methyl homologues thereof; andD803 is an oil-insoluble green petroleum sulfonic acid radical.

Halogen non T" wherein 'T is a hydrocarbon' radical having at least 8and not more than 32 carbon atoms, and

T is a member of the clas consisting ofhydrogen atoms, hydrocarbonradicals having less than 8 carbon atoms, and hydrocarbon radicalshaving at least 8 and not more than'32 carbon atoms; and D'EN representsa heterocyclic compound of the pyridine series consisting of pyridine,quinoline, isoquinoline, and C-linked methyl .homologues thereof; andD803 is an oil-insoluble green petroleum sulfonic acid radical.

D S O a N a1kylene.00C.R

alkyleneN in which RC0 is the acyl radical of a low molar monocarboxyacid having 5 carbon atoms or less,

and R'CO is the acyl radical of a detergent-forming monbcarboxy acidhaving at least 18 and not more than .32 carbon atoms; and-'D'ENrepresents a heterocyclic compoundof 'the pyridine series consisting ofpyridine, quinoline, isoquinoline, and C-linked methyl homologuesthereof; and D80: is an oil-insoluble green petroleum sulfonic acidradical. I

As previously. stated, the manufacture of these compounds representsnothing more than following thesame procedure referred todn the pre--ceding patent and the aforementioned co-pending applications andpatents, except that instead of neutralizing pyridine or a similarcompound with hydrochloric acid or the equivalent, one employs awater-soluble petroleum sulfonic acid, of the green acid type, as hereindescribed. Such green petroleum acids may be obtained from paraflin typecrudes, or naphthene type crudes, or from asphaltic type crudes, ormixed type crudes. It is understood that all the various reactantsreferred to in the above patent and the aforementioned co-pendingapplications may be used; and this statement applies with the same forceand efiect as if they were repeated in detail here. It is also obviousthat compounds can be obtained by double decomposition, for instance,reactin the Dyridinium chloride with a sodium sulfonate in alcoholicsolution, so as to precipitate sodium chloride. 7 i

For the sake of brevity, reference will immepetroleum distillates orpetroleum fractions, and

in some instances, they are produced from the crude petroleumitself.When produced from crude petroleum itself, it is customary to use crudeoil of the naphthenic type, crude oil of the paraffin type, crude oil ofthe asphaltic typ and mixtures of said three difierent types of crudeOil.

The art of refining crude petroleum or various fractions, using sulfuricacid of various strengths, as well as monohydrat and fuming acid, is awell known procedure. In such conventlonal refining procedure, petroleumsulfonic acids have been produced as by-products. For

instance, in removing the oleflnic components, it

has been common practice to use sulfuric acid so as to polymerize theolefines or convert them into sulfonic acids which are subsequentlyremoved. Likewise, in the production ofwhite oil,

or highly refined lubricating oils, it has been customary to treat withfumingsulfuric' acid,

so as to eliminate certain undesirable compo-- nents.

In recent years, certain mineral oil fractions have been treated withsulfuric acid with the primary object of Producing petroleum sulfonic'acids, and insuch procedure, the petroleum sulfonic acids representedthe primary products of reaction, rather than concomitant by-products.

Petroleum sulfonic acid, regardless of whether derived as the principalproduct of reaction or as a by-product, can 'be divided into two generalproducts, to wit,green acid or acids and mahogany acid oracids. Thegreen acids are characterized by being water-soluble or dispersible. Inother words, they form either true solutions or sols. For purpose ofconvenience, they will be herein referred to as water-soluble, withoutany effort to indicate whether the solution is molecular or colloidal innature. The green acids,

as indicated by their name, frequently give an aqueous solution having adark green or graygreen, appearance. They generally appear as acomponent of the acid draw-off, and do not remain behind dissolved inthe on fraction which has been subjected to sulfuric. acid treatment.

The green acids are notsoluble in oil, even when substantiallyanhydrous, and certainly are not soluble in oil when they contain asmuch as 15% of water. Similarly, their salts obtained by neutralizingthe green acids with a strong solution of caustic soda, caustic potash,or ammonia, are not oil-soluble. For convenience of classification, theammonium salt will be considered as an alkali salt.

In contradistinction to the hydrophile green acids, there occurs, as inthe manufacture of medicinal white oil, the oil-soluble type of themahogany acids. These mahogany acids are characterized by being solublein oil, especiallywhen anhydrous, and being soluble in oil, even if theycontain some dissolved water. Some of the mahogany acids also showlimited hydro philic properties to the extent that either some water canbe dissolved in the acids, or they, in turn, may dissolve tosome extentin water. In some instances, their salts, such as the sodium, ammonium,or potassium salt, will dissolve in water to give a colloidal sol.However, regardless of the presence of any hydrophilic propertieswhatsoever, they always have a characteristic hydrophobe property, asindicated by the fact that the substantially anhydrous form, forinstance, their alkali salts containing 5-12% water, will dissolve inoil. This clearly distinguishes them from the green acids previouslyreferred to, because the green acids in similar form con taining thesame amount of water, for example, will not dissolve in oil. The greenacids, as such, are essentially hydrophilic and non-hydrophobic incharacter.

As is previously indicated, we have found that if green acids of theoil-insoluble type are converted into amido pyridinium salts, of thekind herein described, the resulting product has pronounced value as ademulsifier for oil field emulsions of the water-in-oil type, eitherwhen used alone, or in conjunction with other compatible and well knowndemulsifying agents. a i

The hydrosulfonate employed is conveniently obtained by neutralizing thepyridine bases with green petroleum acids. As to methods "of preparingthe green petroleum acids, the following example are included in orderto illustrate the various types which may be employed:

Example A Green acids are obtained from Gulf Coast lubricating oildistillate having an S. U. viscosity at 150 F. of about 400 seconds. Theprocedure employed in obtaining such green acids is that described in U.S. Patent No. 2,188,770, dated January 30, 1940, to Robertson. Thematerial so Example B The same procedure is followed as in Example A,but instead, the green acids are obtained from Gulf Coast transformeroil extract in the manner described in U. S. Patent No. 2,203,443, datedJune 4, 1940, to Ross and Mitchell.

Example C The same procedure is followed as in Example B, except thatCalifornia 65 Saybolt viscos ty Edeleanu extract is employed instead ofGulf Coast transformer Edeleanu extract employed in Example B.

Ewample D The same procedure is followed as in Example A, except thatthe product is made from a Gulf Coast naphthene type crude, preferablyof the kind which has little or no low boiling fraction, i. e., the kindwhich, on a straight run distillation, gives little or no gasoline.

In the following examples it will be noted that they are substantiallyin verbatim form as they appear in the aforementioned patents and co-Example 1 500 g. of a fatty acid ethanolamide, obtained by reaction ofsplit cocoanut oil (containing all the natural acids, beginning with thecaprylic up to the stearic acid, and some oleic acid) withmonoethanolamine, 630 g. hydrosulfonate of a fraction of pyridine bases(50% distilling up to 140 C., distilling up to 160 0., completelysoluble in water) and g. of the mixture of the free pyridine bases, areheated at 100 C., or even higher, for one-half to five hours.

When working at -160" C., the reaction is more rapid.

Furthermore, pure pyridine may be used instead of a mixture of pyridinebases. (Compare with Example 2 of Haack Patent No. 2,242,211.)

The hydrosulfonate employed is conveniently obtained by neutralizing thepyridine bases with agreen sulfonic acid of the kind describedimmediately preceding. (Compare also with Example 1 of U. S. Patent No.2,273,181.)

Example 2 One pound mole of octyllactamide '(derived by reaction betweenoctylamine and ethyl lactate) is reacted with 1.1 pound moles ofpyridine hydrosulfonate in the presence of one-twentieth of a mole offree pyridine. The reaction is conducted at approximately 150-160" C.,until the substituted lactamide has been converted into the quaternarycompound. This reaction is complete in a comparatively short time, insome instances less than one hour, although in other instances three orfour hours may be required. If desired. the reaction may be conducted ata slightly higher temperature, for instance, as high as 180 C. Insteadof using pyridine hydrosulfonate, one may employ the hydrosulfonate of afraction of pyridine bases of the kind that 50% will distil over at 140C., or below, and 90% at C., or below. Such selected pyridine bases areof the kind wh ch are entirely water-soluble. The hydrosulfonateemployed is obtained by neutralizing the pyridine bases with greensulfonic acid of the kind described previouslv. (Compare w th ourco-pending application Serial No. 4 5.766. filed October 20, 1941. now1'). S. Patent No. 2,329,703, dated September 21, 1943.)

Example 3 tained. The reaction mixture is then distilled at 60-70 C.,under reduced pressure, to remove The hydrosulfonate employed isobtained by neutralizingthe pyridine bases with the same green sulfonicacid as employed in previous examples. (See U. S. Patent No. 2,290,417,dated July 21, 1942, to De Groote and Keiser. See also Example 2 of U.S. Patent No. 2,146,392, to Baldwin et a1.)

Example 4 570 grams of a fatty acid diethanolamide, obtained by reactionof split cocoanut oil (containing all, the natural, acids, beginningwith the capric up to stearic, and some oleic), with di-, ethanolamine,710 g. of hydrosulfonate of a fraction of pyridine bases (50%distillingiup to 140 C., 90% distilling up to 160, completely soluble inwater), and 100 g. of the mixture of the free pyridine bases, are heatedat 100 C. for about 4 hours.

When working at 150-l60f, the reaction is more rapid.

Furthermore, pure pyridine may be used instead of a mixture of pyridinebases. (Compare with Example 2 of the aforementioned Haack Patent No.2,242,211.)

The hydrosulfonate employed is obtained by neutralizing the pyridinebases with the same green sulfonic acid as employed in previousexamples. (Compare also with our co-pending application Serial No.415,763, filed October 20, 1941, now U. S. Patent No. 2,329,700, datedSeptember 21, 1943.

- Ezrample 5 360 g. of a fatty acid amide, obtained by reactionof splitcocoanut oil (containing all the natural acids, beginning with thecapric up to the stearic acid, and some oleic acid) withtris(hydroxymethyl)aminomethane,, 429 g. hy-

, drosulfonate of a fraction of pyridine bases (50% distilling up to 140C., 90% distilling up to 160 C., completely soluble in water) and 100 g.of the mixture of the free pyridine bases, are heated at 100 C. forabout five hours.

The hydrosulfonate employed is obtained by neutralizing the pyridinebases with the same green sulfonic acid as employed in previousexamples. (Compare with our co-pending application Serial No. 415,764,filed October 20, 1941, now U. S. Patent'No. 2,329,701, dated September21, 1943, Example 1.)

Example 6 One pound mole of the amide derived from mixed cocoanut oil isreacted with 4 pound moles f ethylene oxide to give an amidecorresponding to the following formula wherein R.CO represents the acylradical of the mixed cocoanut oil fatty pletely soluble in water, may beemployed as a reactant. The hydrosulfonate employed is obtained byneutralizing the pyridine bases with the same green sulfonic acid asemployed in previous examples. (Compare with Example 2 of the iaforementioned Haack Patent No. 2,242,211.

Compare also with our co-pending application Serial No. 415,765, filedOctober 20, 1941, now

U. 8. Patent No. 2,329,702, dated September 21, 1943.)

Example 7 One pound mole of the esteramide derived by reaction betweenequimolar portions of bis(hydroxyethyl) acetamide and ricinoleic acid isheated with 1.05 moles of pyridine hydrosulfonate at 140- 150 C. Thetime required is generally less than one hour, and the reaction ishastened by the presence oi a small amount, 1% or 2%, of free pyridine.Ii'desired, the reaction may be conducted at a slightly highertemperature, for instance, ISO-170 C. Instead of using pyridinehydrosulfonate, one may'employ the hydrosulfonate of a fraction ofpyridine bases, of the kind that 50% would distil over 140 C., or below,and 90% at 160 C. or below. Such selected pyridine bases are of the kindwhich are entirely water-soluble. The hydrosulfonate employed isobtained by neutralizing the pyridine bases with the same green sulfonicacid as employed in previous examples. (Compare with our co-pendingapplication Serial No. 419,082, filed November 14, 1941, now U. S.

reactants. Instead of pure pyridine, a mixture of pyridine bases, forinstance, 50% distilling up to 0., and 90% distilling at C., and com-Patent No.2,335,262, dated November 30, 1943, Example 1.)

Example 8 The same procedure is followed as in Examples 1-7, preceding,except that instead of employing a green sulfonic acid of the kindexemplified by Example A, preceding, one employs a green sulfonic acidof the kind employed by Example B, C, or D, preceding.

The general method of manufacture is obvious, in view of what is said inthe aforementioned patents and the aforementioned co-pendingapplications, and also in the light of the above illustrations.Generally speaking, the convenientv procedure is as follows:

(a) Prepare a suitable oil-insoluble green sulfonic acid, for instance,the kindillustrated in Example A, preceding, and most preferably, inanhydrous, or substantially anhydrous, form. If too viscous forapparatus available, or in any instance, dilute conveniently with a highboiling solvent.

(b) Neutralize pyridine or a selected pyridine base with such sulfonicacid, using equivalent molal proportions. I

(0) Obtain a high molal amide of any one of the types previouslysuggested, for instance,

amides derived from a high molal monocarboxydetergent-forming acid and ahydroxylated primary or secondary amine; or an amide derived from a lowmolal hydroxy acid, particularly lactic acid, and an amine such asoctadecylamine, or a hydroxylated amide of a low molal non-hydroxy acid,such as acetic acid, and esterify the hydroxyethyl group or'the likewith a high molal for instance, an amount of the free base equivalent to25% of the amount present as the hydrosulfonate.

' (f) If the pyridine hydrosulfonate is watersoluble, and if thehydroxylated amide is water'- soluble, or forms a, colloidal sol, thenif reaction results in an insoluble product, the very formation of suchproduct indicates completeness of reaction, However, this index is notentirly satisfactory for a number of reasons. In the first, place, thepyridine hydrosulfonate may not be watersoluble to any marked degree. Inthe second place, the pyridine hydrosulfonate may be obtained from a;sulfonic acid which has present some inert high boiling solvent whichimparts water-insolubility to the mixture. Finally, even though thereaction involved produces an insoluble product, the presence of eitherreactant in slight excess may act as a peptizing agent and produce asolution or sol. Similarly, there may ,be present an impurity which doesnot enter into the reaction at all, and yet acts as a peptizing agentand produces a solution under conditions which would ordinarilysuggest'formation of an insoluble precipitate.

For this reason, completeness of reaction is best predicated upon othertests. If the reaction time is continued from two to five hours, andparticularly, if the longer period is employed at a temperature of180-200 0., reaction is generally complete. Secondly, if thereactionmass is purified; a molecular weight determination will show thatreaction has taken place insofar that the -molecular weight of theresultant is equal to the sum of the molecular weight of the tworeactants.

A small amount of the reaction mass may be acidified with HCl so as toconvert uncombined pyridine into the hydrochloride.

An acidic pyridine hydrochloride solution can be treated with causticand pyridine liberated or determined in any suitable manner. The amountof pyridine remaining in the reaction mass is an index, of course, tothedegree to which the reaction has taken place.

Instead of using the above procedure, one may use the method of doubledecomposition. This depends on forming the pyridinium hydrochlo-' ride,not the hydrosulfonate, and obtaining the quaternary compound in thechloride or equivalent form, as described in aforementioned U. S. PatentNo. 2,273,181, and also in the various aforementioned copendingapplications. Having obtained the quaternary chloride or equivalent, ifit is water-soluble, then one need only prepare an aqueous solution.Similarly, one prepares an aqueous solution of the selected greensulfonic acid salt, for instance, the sodium, ammonium, or potassiumsalt, of a green acid of the kind illustrated by Example A, preceding.These two aqueous solutions are mixed in molar proportions, Aprecipitate is formed and sodium chloride or potassium chloride orammonium chloride passes into the water phase and can be discarded. Hereagain, precaution must be taken that the mixture of the two reactions,or rather, that the resultant is not rendered water-soluble by peptizingaction, as previously described.

Another satisfactory procedure is to use the double decomposition methodby employing anhydrous materials dissolved in absolute alcohol or itsequivalent. When the two solutions are mixed, sodium chloride isprecipitated and the resultant stays dissolved in the alcohol.Filtration or decantation can be employed to remove the insoluble saltsuch as sodium chloride and organic acids containing eight carbon at I Wmore, and not more than 32 carbon atoms, are

the alcohol can be evaporated from the resultant and re-used in furthermanufacture. 7 It is to be noted that the various reactants employed forproducing compounds of the kind herein contemplated include thefollowing: Monccarboxy detergent-forming acids; high molal amines;hydroxylated primary and secondary amines; low molal hydroxy acids, suchas lactic acid; non-hydroxylated low molal acids, such as acetic acid,butyric acid, etc., having. less than 8 carbon atoms; aldehydes, andparticularly, formaldehydeithe aldehydes can be used to re act with highmolal acid amides, such as fs ear amide, to produce a hydroxymethylstearainr )1 It is well known that certain monoc'arb'o'xy s orcharacterized by the fact that they combine with alkalies to producesoap 'or soap-lik materials These detergent-forming acids include "fattyacids, resin acids, petroleumacids, etc. For the sake of convenience,these acids will be'indicat ed by the formula R.COOH. Certainderivatives-of detergent-forming acids react with alkali to pro ducesoap or soap-like materials, and are the ob vious equivalent of theunchangedor'unmodified detergent-forming acids; for instance, instead offatty acids, one might employ the chlorinated fatty acids. Instead ofthe resin acids, one might employ the hydrogenated resin acids. Insteadof naphthenic acids, one might employ brominated naphthenic acids, etc.

The fatty acids are of the type commonly referred to as higher fattyacids; and of course, this is also true in regard to derivatives of thekind indicated, insofar that such derivatives are obtained from higher.fatty acids. The petroleum acids include not only naturally-occuringnaphthenic acids, but also acids obtained by the oxidation of wax,parafin, etc. Such acids may have as many as 32 carbon atoms. Forinstance, see U. S. Patent No. 2, dated y 0. 1941, to Shields.

The low molal non-hydroxy monocarboxy acids include acetic acid,propionic acid, butyric acid, valeric acid, etc.

Hydroxyalkyl ether radicals may be obtained from oxyalkylated amides.For'instance, a high molal carboxy acid or its functional equivalent,such as the ester, acyl chloride, anhydride, etc., may be reacted with aprimary or secondary hydroxylated amine, such as monoethanolamine.diethanolamine, monopropanolamine, dipropanolamine, tris(hydroxymethyl)aminomethane, etc. The amide so obtained is treatedwith an oxyalkylatingagent containinga reactive ethylene oxide ring, such as ethylene oxide,butylene oxide, glycid, etc. The amides derived from low molal acids canbe similarly treated; for instance, the amides derived from lactic acid,acetic acid, etc.

Other suitable amines used as reactants for amidification include:2-amino-1-butanol; 2- amino-2-methyl-l-propanol; 2-amino-2-methyl- 1,3-propane diol; 2-amino-2-ethyl-1,3-propane diol tris (hydroxymethyl)aminomethane.

Instead of using monoethanolamine, diethanolaminaor the like, one mayuse compounds such as' amyl' ethanolamine, cyclohexyl ethanolamine,benzyl ethanolamine, etc. In some instances, the amides arepreferentially obtained by reacting the high molal acid, for instance, ahigher fatty acid, with cyclohexylamine, amylamine, benzylamine,aniline, or the like, and then treating the amide with ethylene oxide orthe like so as to introduce a hydroxya ethyl group. As to the productionof hydroxytive hydroxyl, reference is made to U. S. Patent No.2,246,842, dated June 24, 1941, to De Groote. It is to be noted thatthat particular patent excludes arylamines; but it is understood thatsuch compounds are not excluded in the present instance. For instance,naphthylamine, methyl n'aphthylamine, ethyl, naphthylamine, and the'like, may be employed.

Furthermore, attention is directed to the fact I that saidaforementioned De Groote patent contemplates, inter alia, certaintertiary amines. Such amines, of course, are not hereincontemplated asreactants, insofar that there is no reactive hydrogen atom available.

The primary amines which may be used as such or converted into secondaryamines by con-- ventional processes, such as treatment with methyliodide, benzyl chloride, alkyl sulphates, or the like, decenylamine;cetylamine; stearlyamine; oleoamine; ricinoleoamine; amines derived fromnaphthenic acids; amines derived from octa- 'decadiene 9,11-acid-1;octztdecylamine; amines derived from mixed unsaturated fatty acids, suchas soyabean fatty acids; cottonseed oil fatty acids; linseed oil fattyacids; heptadecylamine,

hexadecylamine; dodecyla-mine; decylamine, etc.

The amines may be aliphatic, aralkyl, alicyclic,

: aryl, alkyl, etc.

One, may also employ amines derived from acids obtained by oxidation ofwax, paraiiin, etc. Such acids may haveas many as 32 carbon atoms. Forinstance, see U. S. Patent No. 2,242,837, dated May 20, 1941, toShields. The

following patents listed in the aforementioned- De Groote Patent No.2,246,842 are herein ininclude the following: Octachloride, sulfurdioxide extract obtained in the refining of petroleum, etc., maybeemployed as diluents. Similarly, the material or materials employed asthe demulsifying agent of our process may be admixed with one or more ofthe solvents customarily used in connection with conventionaldemulsifying agents. Moreover, said material or materials may beusedalone, or in admixture with other suitable well known classes ofdemulsifying agents.

It is well known that conventional demulsifying agents may be used in awater-soluble form, or in an oil-soluble form, or in a form exhibitingboth oil and water solubility. Sometimes they may be used in a formwhich exhibits relatively limitedoil solubility. However, since suchrecluded as a matter of convenience indicating means of obtaining suchhigh molal primary or secondary amines, or methods which can beobviously modified to produce the same: U. S. Patents Nos. 1,951,469,dated March 20, 1934, Bertsch: 2,006,058, dated June 25, 1935, Olin;2,033,866, dated March 10, 2,074,830,'dated March 23, 1937, Flett;2,078,922, dated May 4, 1937, Arnold; 2,091,105, dated Aug. 24, 1937,Piggott;'2,108,147, dated Feb. 15, 1938, Speer; 2,110,199, dated March8, 1938, Carothers; 2,132,902, dated Oct. 11, 1938, Lenher; 2,178,522,dated Oct. 31, 1938, Ralston; British Patents Nos.

359,001, of 1932, to Johnson; and 358,114, of

1932, to Carpmaell Conventional demulsifying agents employed in thetreatment of oil field emulsions are used as such, or after dilutionwith any suitable solvent,

such as water, petroleum hydrocarbons, such as gasoline, kerosene, stoveoil, a coal tar product, such as benzene, toluene, xylene, tar acid oil,cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols,such as methyl a1- cohol, ethyl alcohol, denatured alcohol, propylalcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may beemployed as diluents. Miscellaneous solvents, such as pine Oil, carbontetra-.-

1936, Schrauth;

agents are sometimes used in a ratio of 1 to 10,000, or 1 to 20,000, oreven 1 to 30,000, such an apparent insolubility in oil and water is notsignificant, because said reagents undoubtedly have solubility withinthe concentration employed. This same fact is true in regard to thematerial or materials employed as the demulsifying agent of our process.

In practising our process, a treating agent or demulsifying agent of thekind above described is brought into contact with or caused to act uponthe emulsion to be treated, in any one of the various ways, or by any ofthe various apparatus now generally used. to resolve or break petroleumemulsions with a chemical reagent, the

above procedure being used either alone or in combination with otherdemulsifying procedure, such as the electrical dehydration process.

The demulsifier herein contemplated may be employed in connection withwhat is commonly known as down-the-hole procedure, 1. e., bringing thedemulsifier in contact with the fluids of the well at the bottom of thewell, or at some point prior to their emergence. This particular type ofapplication is decidedly feasible when the demulsifier is used inconnection with acidification of calcareous oil-bearing strata,especially if suspended in or dissolved in the acid employe foracidification.

It may be that some green sulfonic acids have more than one sulfonicacid radical. In such instances, at least 'one sulfonic acid radicalwould have to be neutralized with the amido pyridinium base hereindescribed. The other sulfonic acid radical could be so neutralized, orneutralized with some other base, such as caustic soda, caustic potash,ammonium hydroxide, etc. For the sake of convenience, the heretoappendedclaims are concerned with monosulfonic acids and are being obtained froman oil-insoluble green petroleum sulfonic acid; and the amido pyridiniumbase cation being of the following formula:

in which D'EN represents a radical derived from a heterocyclic compoundof the pyridine series, consisting of pyridine, quinoline, isoquinoline,and C-methyl linked homologues thereof; and X is a divalent aliphaticradical; and Y is a member of the class consisting of acyl radicals,hydrocarbon radicals having not over 22 carbon atoms, alkylol radicals,hydroxylated aliphatic ether radicals, acylated alkylol radicals, andacylated hydroxylated aliphatic ether radicals; Z is a member of theclass consisting of hydrogen atoms, acyl radicals, hydrocarbon radicalshaving not over 22 carbon atoms, alkylol radicals, acylatedalkylol-radicals, hydroxylated aliphatic ether radicals, and acylatedhydroxylatecl aliphatic ether radicals; with the added proviso thatthere must be an acyl radical directly linked to the trivalent nitrogenatom; and there must be 'present at least one hydrocarbon radicalcontaining at least 8 and not more than 32 carbon atoms as an integralpart of at least one 'of the radicals linked to the trivalent nitrogenatom.

troleum sulfonic acid; and the amido pyridinium base cation being of thefollowing formula:

in which D'EN represents a radical derived from a heterocyclic compoundof the pyridine series, consisting of pyridine, quinoline, isoquinoline,and C -methyl linked homologues thereof; and X is a divalent aliphaticradical; and Y is a member of the class consisting of acyl radical,hydrocarbon radicals having not over 22 carbon atoms, alkylol radicals,hydroxylated aliphatic ether radicals, acylated alkylol radicals, andacylated hydroxylated aliphatic ether radicals; and Z is a member of theclass consisting of hydrogen atoms, acyl radicals, hydrocarbon radicalshaving not over 22 carbon atoms, alkylol radicals, hydroxylatedaliphatic ether radicals, acylated alkylol radicals, and acylatedhydroxylated aliphatic -ether radicals; with'the added proviso thatthere must be an acyl radical linked to the trivalent nitrogen atom, andthere must be present at least one hydrocarbon radical containing atleast 8 and not more than 32 carbon atoms as an integral part of atleast one of the radicals linked to the trivalent nitrogen atom.

3. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action ofa demulsifyingagent containing the salt of an amido pyridinium base; said amidopyridinium base salt being obtained from an oil-insoluble greenpetroleum sulfonic acid derived from a naphthene type crude; and theamido pyridinium base cation being of the following formula:

in which DEN represents a radical derived from a heterocyclic compoundof the pyridinium series, consisting of pyridine, quinoline,isoquinoline, and C-methyl linked homologues thereof; and X is adivalent aliphatic radical; and Y is a member of the class consisting ofacyl radicals, hydrocarbon radicals having not over 22 carbon atoms,alkylol radicals, hydroxylated aliphatic ether radicals, acylatedalkylol radicals, and acylated hydroxylated aliphatic ether radicals;and Z is a member of the class consisting of hydrogen atoms, acylradicals, hydrocarbon radicals having not over 22 carbon atoms, alkylolradicals, hydroxylated aliphatic ether radicals, acylated alkylolradicals, and acylated hydroxylated aliphatic ether radicals; with theadded proviso that there must be an acyl radical linked to the trivalentnitrogen atom, and there must be present at least one I hydrocarbonradical containing at least 8 and not more than 32 carbon atoms as anintegral part of at least one of the radicals linked to the trivalentnitrogen atom.

4. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifyingagent containing the salt of an amido pyridinium base; said amidopyridinium base salt being obtained from an oil-insoluble greenpetroleum sulfonic acid derived from a paraflin type crude; and theamido pyridinium base cation being of the following formula:

in which D'EN represents a radical derived from a heterocycliccompoundof the pyridine series, consisting of pyridine, quinoline,isoquinoline, and C-methyl linked homologues thereof; and X is adivalent aliphatic radical; and Y is a member of the class consisting ofacyl radicals, hydrocarbon radicals having not over 22 carbon atoms,alkylol radicals, hydroxylated aliphatic ether radicals, acylatedalkylol radicals, and acylated hydroxylated aliphatic ether radicals;and Z is a member of the class consisting of hydrogen atoms, acylradicals, hydrocarbon radicals having not over 22 carbon atoms, alkylolradicals, hydroxylated aliphatic ether radicals, acylated alkylolradicals, and acylated hydroxylated aliphatic ether radicals; with theadded proviso that there must be an acyl radical linked to the trivalentnitrogen atom, and there must be present at least one hydrocarbonradical containing at least 8 and not more than 32 carbon atoms as anintegral part of at least one of the radicals linked to the trivalentnitrogen atom.

5. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifying agent containin the salt of an amido pyridinium base; said amidopyridinium base salt being obtained from an oil-insoluble greenpetroleum sulfonic acid derived from an asphaltic type crude; andtheamido pyridinium base cation being of the following formula:

divalent aliphatic radical; and Y is a member of the class consisting ofacyl radicals. hydrocarbon radicals having not over 22 carbon atoms,alkylol radicals, hydroxylated aliphatic ether radicals, acylatedalkylol radicals, and acylated hy'dromlated aliphatic ether radicals;and Z is a. member of the class consisting of hydrogen atoms, acylradicals,

hydrocarbon radicals having not over 22 carbon atoms, alkylol radicals,hydroxylated aliphatic ether radicals, acyiated alkylol radicals, and

acylated hydroxylated aliphatic ether radicals; with the added provisothat there must be an my! radical linked to the trivalent nitrogen atom,and there must be present at least one hydrocarbon radical containing atleast 8 and not more than 32 carbon atoms as an integral part of atleast one of the radicals linked to the trivalent nitrogen atom.

MELVIN DE GROOTE. BERNHARD KEISER;

